Silver-free low-E solar control coating

ABSTRACT

A multi-layer, low-emissivity, solar control article comprises a dielectric substrate, a first dielectric metal oxide layer deposited on the substrate, a first highly conductive, silver-free metal oxide layer deposited on the first dielectric metal oxide, and a second dielectric metal oxide deposited on the first highly conductive, silver-free metal oxide layer. The aforementioned coating layer sequence may be repeated as necessary to achieve the desired properties. An iridescence suppressing interlayer may, optionally, be utilized in connection with the low-emissivity, solar control coating.

BACKGROUND OF THE INVENTION

Conventionally, solar control, low-e films made by various depositionprocesses, e.g., sputtering, have consisted of one or more layers of aconductive metal, such as silver, sandwiched between layers ofdielectric materials. The dielectric materials isolate the conductivemetal layer(s) and prevent, or at least minimize, undesirable oxidationof the conductive metal. While such film stacks, in variousconfigurations, have been found to provide coatings exhibiting goodlow-emissivity and solar control properties, they are also known to havepoor chemical and mechanical durability, thus increasing the risk ofdamage to the coating from exposure to atmospheric humidity orscratching from normal handling activities.

Improvement of the physical and chemical durability of silver-containingfilms has been attempted by others. These effects include varying thecomposition of the dielectric layers, dividing individual dielectriclayers into sub-layers of different dielectric materials, alloying thesilver with other metals, and various methods of modifying so-called“sacrificial” layers between the silver and dielectric layers.

Thus, those skilled in the art of thin film design and coated productmanufacturing have continued to search for a thin film structure whichhas good emissivity and solar control properties, but which is superiorin both chemical and mechanical durability.

SUMMARY OF THE INVENTION

The present invention comprises a low-emissivity, solar control coatingdeposited on a dielectric substrate, the coating comprising a firstdielectric metal oxide layer deposited on the dielectric substrate; afirst highly conductive, silver-free metal oxide layer deposited on thefirst dielectric metal oxide, the highly conductive metal oxide havingan electrical conductivity greater than 10,000 ohm⁻¹ cm⁻¹; and a seconddielectric metal oxide layer deposited on the first highly conductive,silver-free metal oxide layer.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention utilizes the well-known concept of inducedtransmission filters to form a thin film coating structure comprisingone or more highly electrically conductive metal oxide layers, ratherthan conductive metal layers. The present structure further comprises alayer of a dielectric metal oxide on either side of the highlyconductive metal oxide layer. This sequence of layers may be repeated asnecessary to achieve the emissivity and solar control propertiesdesired.

The choice of the highly conductive metal oxides and the dielectricmetal oxides, as well as the thickness of the layers in which suchoxides are deposited, are important to achieving the sought-aftercombination of low-emissivity, high visible transmission, high IRreflection/absorption, mechanical durability, chemical stability, and inparticular, good solar control.

In this connection, dielectric metal oxides useful for the presentinvention include, oxides of tin, titanium, zinc, bismuth, and alloys ofsuch oxides. Nitrides of silicon may also be useful for the presentinvention. Layer thicknesses of such dielectric metal oxides suitablefor the invention are in the range of 200 to 400 Å, preferably, 250-350521 .

The highly conductive metal oxides useful for the present inventioninclude simple oxides such as oxides of rhenium, ruthenium, iridium,chromium and molybdenum perovskite type mixed oxides, including CaRuO3,SrRuO3, SrVO3, SrCrO3, SrFeO3, SrTiO3, SrMoO3, CaVO3, LaTiO3, Sr₂VMoO₆;spinel type mixed oxides, such as NiCo2O4; heavily doped tungsten oxidebronzes, such as Na_(x)WO3 (where x+>0.40). Layer thicknesses of theaforementioned highly conductive metal oxides suitable for the inventionare less than 1000 Å, preferably less than 500 Å.

Table 1 shows some exemplary electrical resistively and electricalconductivity values for commonly used highly conductive metals, i.e., Agand Cu, as well as highly conductive metal oxides suitable for use inconnection with the present invention, i.e., ReO₃, Na_(0.8)WO₃ and RuO₂.Although the conductivities of the exemplary highly conductive metaloxides are substantially lower than the conductivities of Ag and Cu, themetal oxides shown in Table 1 have been found to perform satisfactorilyfrom an electrical conductivity viewpoint, and to display the otherdesired properties discussed herein which make such oxides superior toAg and Cu for the applications of the present invention.

More specifically, highly conductive metal oxides having aconductivity >10,000 ohm⁻¹ cm⁻¹, and preferably a conductivity >50,000ohm⁻¹ cm⁻¹, are suitable for the present invention.

The conductivities of the highly conductive metal oxides are clearlysuperior to conventional doped metal oxides, such as fluorine-doped tinoxide and tin-doped indium oxide, as can be seen in Table 1.

TABLE 1 Material Resistivity (μohm-cm) Conductivity (ohm⁻¹cm⁻¹) Ag 1.6590,000 Cu 1.7 625,000 ReO₃ 9-18 55,000-110,000 Na_(0.8)WO₃ 80 12,500RuO₂ 40-100 10,000-25,000  SnO₂:F 400 2,500 In₂O₃:Sn 200 5,000

The films formed according to the present invention will, generally,have stoichometry corresponding to the stoichometric oxide of thecorresponding metal, e.g., SnO₂, TiO₂, etc., however, films which areslightly oxygen deficient may also be produced, and may be useful.

Thin film structures utilizing a combination of the above-describeddielectric and highly conductive metal oxides in a three-layer sequencehave been found to exhibit an emissivity of <0.3, preferably <0.1, avisible light transmittance >70%, and a total solar energy transmittanceof <60%. Preferably, the thin film structure will have a total solarenergy transmittance <45%.

The chemical durability of the above-described thin film structures issignificantly improved over conventional structures as, without wishingto be bound by any theory, the inventors believe the highly conductivemetal oxide replacing the silver significantly reduces reaction of thefilm with ambient humidity, atmospheric contaminants, and the like. Theinventors believe that replacement of the silver with a less reactivemetal oxide improves the chemical stability of the film stack.

Similarly, the inventors believe that the mechanical durability of thethin film structure will be improved by replacing the ductile, malleablesilver layer with a rigid, stiff metal oxide layer.

The thin film or coating of the present invention may be deposited onany suitable dielectric substrate material. A transparent glass, made bythe float glass process, particularly a soda-lime-silica glass has beenfound to be suitable. Some tinted glasses may also be suitable.

The films of the present invention may be deposited on theaforementioned substrates by any suitable method, including varioustypes of sputtering or CVD techniques. In particular, an on-linedeposition process occurring during the float-glass manufacturingprocess is considered suitable. A particularly preferred on-linedeposition process for the present invention is atmospheric pressurechemical vapor deposition.

An apparatus, useful for the on-line production of the coated glassarticle of the present invention, generally comprises a float section, alehr, and a cooling section. The float section has a bottom whichcontains a molten tin bath, a roof, sidewalls, and end walls, whichtogether form a seal such that there is provided an enclosed zone,wherein a non-oxidizing atmosphere is maintained, as hereinafterdescribed in greater detail, to prevent oxidation of the tin bath.During operation of the apparatus, molten glass is cast onto a hearth,and flows therefrom under a metering wall, then downwardly onto thesurface of the tin bath, from which it is removed by lift-out rolls andconveyed through the lehr, and thereafter through the cooling section.

A non-oxidizing atmosphere is maintained in the float section byintroducing a suitable gas, such as for example one composed of 99percent by volume nitrogen and 1 percent by volume hydrogen, into wherethe coating occurs, through conduits which are operably connected to amanifold. The non-oxidizing gas is introduced into the coating zone fromthe conduits at a rate sufficient to compensate for losses of the gas(some of the non-oxidizing atmosphere leaves the zone by flowing underthe end walls), and to maintain a slight positive pressure, convenientlyabout 0.001 to about 0.01 atmospheres above ambient pressure. The tinbath and the enclosed zone are heated by radiant heat directeddownwardly from heaters. The heat zone is generally maintained at atemperature of about 1200° F. The atmosphere in the lehr is typicallyair, and the cooling section is not enclosed. Ambient air is blown ontothe glass by fans.

The apparatus also includes gas distributors located in the float zone.The desired precursor mixtures for the individual coatings are suppliedto the respective gas distributors, which in turn direct the precursormixtures to the hot surface of the glass ribbon. The precursors react atthe glass surface to form the desired coatings.

Optionally, the thin film or coating of the present invention includesunderlayers deposited between the glass substrate and inducedtransmission filter stack. The coatings are such as to provide a barrierto sodium diffusion from the glass into the coating or to provideneutral color in transmittance and reflectance when applied to a clearglass substrate.

The term “silver free”, as used herein, is used to indicate that at mosttrace amounts of silver are present, i.e. less than 0.1 mol % silver.

U.S. Pat. No. 5,798,142 discloses a silica barrier layer and a floatglass production process which may be used in embodiments of the presentinvention. US Pat. No. 5,798,142 is hereby incorporated by reference asif set forth in its entirety herein.

U.S. Pat. Nos. 4,187,336; 4,419,386 and 4,206,252 disclose colorsuppression layers which may be used in embodiments of the presentinvention. US Pat. Nos. 4,187,336; 4,419,386,and 4,206,252 are herebyincorporated by reference as if set forth in its entirety herein.

The following predictive examples show expected transmission in thevisible range (T_(vis)) and transmission in the solar range (T_(sol))according to the present invention. Glass thickness is given in inchesand coating thicknesses are given in Angstroms.

Tvis Tsol Emissivity glass(0.231)/175 SnO2/50 74 59 RuO2/200 SnO2glass(0.231)/400 TiO2/300 71.5 40.2 RuO2/330 TiO2 glass(0.231)/250TiO2/280 84 56.2 0.19 ReO3/250 TiO2

In accordance with the provisions of the patent statutes the presentinvention has been described in what is considered to represent itspreferred embodiment. However, it should be noted that the invention canbe practiced otherwise than as specifically illustrated and describedwithout departing from its spirit or scope.

1. A coated glass article comprising: a dielectric substrate; a firstdielectric metal oxide layer deposited over the dielectric substrate,the first dielectric metal oxide layer comprising an oxide of tin ortitanium; a first highly conductive silver free metal oxide layerdeposited over the first dielectric metal oxide, the highly conductivemetal oxide comprising an oxide of rhenium or ruthenium, having athickness <1,000 Å and an electrical conductivity greater than 10,000ohm⁻¹ cm⁻¹; and a second dielectric metal oxide layer deposited over theconductive, silver-free metal oxide layer, the second dielectric metaloxide layer comprising an oxide of tin or titanium; wherein the coatedglass article has an emissivity of less than 0.3, a visible lighttransmittance >70%, and a total solar energy transmittance of <60%. 2.The solar control coating defined in claim 1, wherein the first highlyconductive metal oxide has an electrical conductivity greater than50,000 ohm⁻¹ cm⁻¹.
 3. The solar control coating defined in claim 1,wherein a second highly conductive silver-free metal oxide layercomprising an oxide of rhenium or ruthenium is deposited over the seconddielectric metal oxide layer, and a third dielectric metal oxide layercomprising an oxide of tin or titanium is deposited over the secondhighly conductive silver-free metal oxide layer.
 4. The coated glassarticle defined in claim 1, wherein the emissivity is <0.1.
 5. Thecoated glass article defined in claim 1, wherein the highly conductivemetal oxide comprises an oxide of ruthenium.
 6. The coated glass articledefined in claim 5, wherein: the first dielectric metal oxide layercomprises SnO₂; the first highly conductive silver free metal oxidelayer comprises RuO₂; and the second dielectric metal oxide layercomprises SnO₂.
 7. The coated glass article defined in claim 5, wherein:the first dielectric metal oxide layer comprises TiO₂; the first highlyconductive silver free metal oxide layer comprises RuO₂; and the seconddielectric metal oxide layer comprises TiO₂.
 8. The coated glass articledefined in claim 1, wherein the highly conductive metal oxide comprisesan oxide of rhenium.
 9. The coated glass article defined in claim 8,wherein: the first dielectric metal oxide layer comprises TiO₂; thefirst highly conductive silver free metal oxide layer comprises ReO₃;and the second dielectric metal oxide layer comprises TiO₂.